EP1245733B1 - Device and method for mass deacidification, elimination of free acidity of cellulosic material - Google Patents

Device and method for mass deacidification, elimination of free acidity of cellulosic material Download PDF

Info

Publication number
EP1245733B1
EP1245733B1 EP00931289A EP00931289A EP1245733B1 EP 1245733 B1 EP1245733 B1 EP 1245733B1 EP 00931289 A EP00931289 A EP 00931289A EP 00931289 A EP00931289 A EP 00931289A EP 1245733 B1 EP1245733 B1 EP 1245733B1
Authority
EP
European Patent Office
Prior art keywords
autoclave
elimination
cellulosic materials
free acidity
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00931289A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1245733A1 (en
Inventor
Rogelio Areal Guerra
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universitat Politecnica de Catalunya UPC
Original Assignee
Universitat Politecnica de Catalunya UPC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Universitat Politecnica de Catalunya UPC filed Critical Universitat Politecnica de Catalunya UPC
Publication of EP1245733A1 publication Critical patent/EP1245733A1/en
Application granted granted Critical
Publication of EP1245733B1 publication Critical patent/EP1245733B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/18—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00 of old paper as in books, documents, e.g. restoring

Definitions

  • the present invention relates to a device and method for mass deacidification of cellulosic materials, with elimination of free acidity of the treated matter, specifically designed for conservation and treatment of books, documents, newsprint, maps, cellulosic fabrics and graphic work on paper, which provides a great efficiency in both safety and quality, as well as significant energy savings and a greater degree of automation as it incorporates an robot which controls the process and a display which allows to view its development.
  • the device and method of the invention are particularly well suited for solving the problems of libraries and archives holding documents of a certain age, preferably from the end of the 18th Century to the year 1960, specifically to conserve and preserve these, obtaining an adequate durability over time.
  • Mass deacidification methods previously tested coincide in their objective of reducing costs with results which are different from those obtained by manual restoration.
  • An hourly wage for a restorer's work in Spain is between 1,800 and 2,000 Pta. in official restoration centres, while a 500 page book requires approximately 70 hours, plus another 15 for sewing and binding. Therefore, a restorer-binder working 1,750 hours a year using odd moments to bind can restore about 20 books a year (between 175,000 and 158,000 Pta./book).
  • Patent application PCT WO 91/04800 FMC Corporation
  • US patent 5.282.320 Wedinggwe et al. describe a machine with a size implying that it cannot be moved, as a book factory, lacking means for efficient dosing and double treatment autoclaves.
  • US patent n° 5.120.500 (Batelle Institute) describes a process for non-polluting deacidification of books and other paper and printed matter of a size similar to that of the FMC design, so that it is a restoration installation comprising a predrying process for these products using high frequency radiation in a vacuum, treatment with solutions for deacidification and later elimination of solvents by vacuum drying with high frequency radiation again.
  • This last type of predrying and final drying have been replaced by conventional means employing heat and vacuum due to the alterations of book pages caused by microwaves, as a result of the mobility of metal particles attached to the surface of the pages.
  • Patent GB 1.582.265 (Batelle Ingenieurtechnik) describes a process in which aged, damaged and fragile paper is treated with a solution containing isocyanate or isocyanate vapour, preferably using isocyanate with two or more isocyanate groups. This system is not related to out invention.
  • a further process with a certain reliability is Bookkeeper from Preservation Technologies, Inc., which uses magnesium oxide with particle size between 0.2 and 0.9 microns and a surfactant acting as a dispersant of the magnesium oxide in the solvent, with perfluoroheptane as solvent.
  • the process consists of a pre-treatment, impregnation and posttreatment.
  • the Sasch process is a variation of the Wei T'o method; its disadvantages is that printed ink will run and white dust is deposited on the bindings. The total alkaline reserve and its distribution is unsatisfactory.
  • Spanish patent n° ES 2.125.792 in the name of the applicant, which relates to a device and method for mass deacidification disinfestation and disinfection of documents and books, employing a solution of a reagent and a suitable solvent HFC R134a; reagents are methoxy and butoxy polyethyleneglycolate magnesium carbonates, which reagents are very similar to those used by the Lithium Corporation of America, but as they were shown to give unsatisfactory results they were discarded after their application in the patented device and replaced by other products. Spanish patent application P9700964 in name of the applicant is a modification of Spanish patent ES 2.125.792.
  • the object of the invention is to disclose a method for mass deacidification and elimination of free acidity which considers environmental factors, that is, which operates in a closed circuit with non-polluting reagents and solvents, complying with the Montreal Protocol and meeting as many conditions as possible for mass deacidification.
  • the device disclosed comprises the features recited in claim 22.
  • the method disclosed by the invention includes the steps as recited in claim 1.
  • the invention provides equipment for the mass deacidification, elimination of free acidity and disinfestation of cellulosic materials; in continuation the invention equipment, which comprises an autoclave (1) with pressure and temperature control into whose interior the cellulosic materials to be treated are introduced.
  • a series of chemical and physical processes are then carried out which produce physical and chemical changes in the substrate of the aforementioned cellulosic materials; a solvent bottle (2) connected to the autoclave (1); a charge cell (13) on which the solvent bottle is placed(2) and which serves to program the quantity of solvent in each process; a dosification tank (8) of concentrated reagent to put in the appropriate quantity of the reagent according to the mass of material to be treated, characterised by having a gravitational collection container (3) for the residual solution coming from the autoclave, (1) for its subsequent recovery.
  • the autoclave (1) comprises a body, for example, cylindrical, and a cover with an airtight joint, a pressure sensor, a safety valve, a temperature control thermocouple in the interior of the autoclave (1), a system for measuring the pressure and the vacuum, an external temperature control and heating bands on the outside wall of the autoclave (1).
  • the solvent bottle (2) contains the solvent and has an external refrigeration system, which, in a specific embodiment, consists of a refrigeration unit made up of a hermetic compressor (C), a condenser and a refrigerated jacket which wraps around the upper section of the solvent bottle (2).
  • the invention equipment could include a de-icing system to eliminate the ice which forms on the jacket covering the solvent bottle (2) which forms during the distillation process.
  • this de-icing system consists of a fan (V) driven by a motor (M) and a heating resistance (R).
  • the previously mentioned refrigerating jacket which wraps around the upper part of the solvent bottle (2) may have a valve for the automatic outflow of condensates.
  • the solvent bottle (2) also has a heating system (10).
  • the dosification tank (8) for concentrated reagent is a container which holds the concentrated deacidification reagent and is connected to the autoclave (1) in such a way that the appropriate quantity of the concentrated reagent can pass directly to the autoclave (1), where it will later reach the desired final concentration by pouring solvent directly from the solvent bottle (2) to the interior of the autoclave (1).
  • the autoclave (1) has a solvent and concentrated reagent input line which is either connected to the concentrated reagent dosification tank (8) or to the pure solvent bottle (2).
  • the gravity collection tank(3) for the residual solution coming from the autoclave (1) allows the collection of this residual solution for later recovery.
  • This tank (3) has a refrigeration system (14) that it uses during the emptying of the autoclave (1).
  • the residual solution collection tank (3) also has a heating system (14) used to distil the solvent contained in the residual solution.
  • the residual solution collection tank (3) has an input for a cleaning product, for example anhydrous n-propanol, or air.
  • the residual solution collection tank (3) also has an evacuation valve (VM7) for the suspension formed after the distillation process.
  • connection between the autoclave (1) and the residual solution collection tank (3) is opened or closed by means of a manual or automatic valve(NV5, VM6).
  • the invention equipment may also include a vacuum pump connected to the autoclave (1), a loading cell (11) on which is placed the dosification tank (8) for the concentrated reagent, a programmable robot for the automatic control of the equipment processes and a touch screen from which the type and steps of the process to be taken are selected, according to the quantity of material to be treated.
  • the invention equipment may include different types of valves, for example:
  • the invention equipment also has the possibility of the availability of a recharging bottle (12) coupled to the system to refill the solvent bottle (2) in the face of losses which may be produced in the course of the process.
  • the invention equipment may have, as a safety precaution, a safety valve in the upper section of the solvent bottle (2), a safety valve in the upper part of the residual solution collection tank (3), and, optionally, a safety valve in the upper section of the autoclave (1).
  • the invention equipment may also include a filter with a humidity absorption indicator in the solvent bottles connection tube(2) with the rest of the system, and comprises a heat exchanger (6) which optimises the refrigeration of the solvent bottle (2) and makes use of the heat produced to heat the residual solution collection tank (3).
  • the invention provides a procedure for the mass deacidification, elimination of free acidity and disinfestation of cellulosic materials.
  • the procedure of the invention by use of the equipment of the invention, which has the following stages:
  • the drying or dehydration of the cellulosic material to be treated is carried out in the autoclave chamber by intermittent cycles of evacuation and the entrance of preferably hot air. To carry out this stage the air is allowed to penetrate into the autoclave chamber and, once it has been introduced, it is heated for the period of time necessary for it to reach a determined temperature, 50° maximum, so as not to damage the material under treatment, increasing the pressure inside the autoclave due to the temperature increase and the closure of the vacuum pump valve.
  • the evacuation cycle is carried out by means of a vacuum pump and a pressure sensor until a vacuum of 30 to 40 millibars is reached.
  • the last cycle in a series of drying or dehydration cycles is a vacuum cycle which leaves the autoclave under a vacuum, used to force the entry of the reagents during the dosification phase.
  • the number of vacuum and air entry cycles is a function of the mass of the cellulosic material.
  • preferably between 10 and 50 vacuum and hot air entry cycles are carried out around 8 minutes to dry or dehydrate a mass of approximately 20 to 60 kilograms(kg) of cellulosic material.
  • the humidity of the cellulosic material is understood to be between 2% and 2,5%.
  • the drying or dehydration procedure used in the invention process is faster than any of those used in other similar processes since at atmospheric pressure and even at lower pressures, in the order of 30 millibars, the thermal conductivity of water vapour is much higher than at high vacuum, at which conventional systems work.
  • This type of dehydration process based on intermittent vacuum/hot air entry cycles, also has some clear distinctions from the conventional systems, given that some of them use high frequency currents. These had to be abandoned owing to the damage caused by the metallic particles within the cellulosic material, or even because of the materials used in the machinery construction.
  • the dosification stage of the active deacidifying product is divided into two sub-stages, (i) a concentrated reagent entry stage, in a specific quantity, from the dosification tank to the lower part of the autoclave, under the action of a vacuum generated in the autoclave in the last drying cycle, in such a way that the concentrated reagent does not come into contact with the cellulosic material; and (ii) a dilution stage of the concentrated reagent to a determined concentration.
  • the active deacidifying product may be any appropriate substance for deacidifying the cellulosic material, optionally accompanied by a suitable carrier.
  • the active deacidifying product is the carbonate of magnesium di-n-propylate, diluted in HFC 227 and a small quantity of n-propanol.
  • the reagent concentration in the dosification tank may vary over a broad range, preferably between 50% and 70% by weight of pure reagent.
  • the concentrated reagent entry stage into the autoclave consists in passing a specific quantity of the aforementioned concentrated reagent from the dosification tank to the lower part of the autoclave.
  • the reagent dilution stage consists of allowing a specific quantity of solvent to pass from the solvent bottle to the autoclave.
  • pouring of the solvent from the solvent bottle to the autoclave is carried out assisted by heating the bottle by means of a heating system, with the aim of encouraging the flow of the solvent to the autoclave.
  • the quantities of concentrated reagent and solvent added to the autoclave are determined as a function of the final concentration of the reagent required, and it is added automatically by means of loading cell pathways on which the concentrated reagent and solvent tanks, respectively, are found.
  • the concentration by weight of the pure reagent after dosification is understood to be between 2.0% and 4.5%, according to the pH of the cellulosic material under treatment.
  • the reagent solution can be programmed by means of loading cells operated by the robot from the concentrated reagent, in order to obtain the previously stated concentrations, which are the most appropriate to provide the paper with alkaline reserves understood to be between 1% and 1.5%.
  • the programming which is carried out as a function of the quantity (kg) and acidity of the cellulosic material under treatment.
  • impregnation of the cellulosic material under treatment stage begins, by contact with a solution of the active deacidifying product in the autoclave chamber.
  • impregnation stage lasts for up to 3 hours according to the weight of the cellulosic material. In this period of time an homogeneous distribution is achieved in the interior of the cellulosic material under treatment, in particular, in the pages of books.
  • the evacuation stage of the residual solution is carried out on completion of the impregnation stage by pouring from the autoclave to the residual solution tank not only by gravity but also by cooling the residual solution tank. Evacuation of the autoclave is also favoured by its heating.
  • the residual solution remaining after the treatment of the cellulosic material contains sludge and solvents, mostly HFC 227.
  • This residual solution may contain a small quantity of spine finishing glues, particularly those after the 1960's, as they are synthetic, magnesium salts, as well as sulphates, chlorides and nitrates and small quantities of n-propanol, besides the dirt of the books that is extracted by the solvent, for example, the HFC 227. These products are deposited at the end, or are dissolved.
  • the liquids under pressure go to the collection tank by gravity and cooling of the system with the system compressor by means of the heat exchanger by opening the corresponding pneumatic valve. Because of this the aforementioned tank is situated in the lower part of the machinery, which includes the invention equipment.
  • the corresponding pneumatic valve is closed so that the vapour of the tank does not flow back towards the autoclave again, at the same time that the residue collector tank is cooled by means of the heat exchanger with the compressor unit.
  • the cellulosic material is collected from the autoclave chamber.
  • the residual liquid collection container is heated by means of a heat exchanger, once the compressor-refrigerator unit, which cools the distillate reception tank is set into operation [that is, the solvent bottle (2)].
  • the treated books are removed from the autoclave chamber and a new batch of books may be put in for dehydration and treatment. Both processes are simultaneous, the duration of the distillation being between 4 and 6 hours, depending on the volume of the solvent used.
  • the drying operation of the cellulosic material takes between 4 and 6 hours, also according to the quantity (kg) of books to be treated, a time which is the same as that of the distillation process.
  • the distillation process is carried out simultaneously with the drying or dehydration procedure of a new batch of cellulosic material to be treated.
  • an opening to the tank from the manual input valve has been provided for the introduction of a cleaning product, for example, n-propanol, and then air is bubbled in to stir and disperse the solid material from the end of the container, giving rise to a suspension that may be eliminated through the evacuation valve of the tank, for example, through a manual valve at the end of the tank.
  • a cleaning product for example, n-propanol
  • the invention process contemplates the possibility of checking for possible loss of weight n the solvent bottle, after a series of processes have been carried out, and the possibility of refilling the solvent if necessary, using an exterior tank that is connected to the aforementioned bottle, in places previously designed for that purpose.
  • the invention process has a result control stage at the end of the procedure.
  • the result control may be carried out by the determination of the distribution of the magnesium (magnesium carbonate) in the treated material before and after treatment. Transverse cuts can be made to see the distribution of the magnesium particles over the length of the cut, using a scanning electron microscope (SEM), and by quantitative determination and identification using electronic microprobe scanning detection and pH determination using a plane electrode on different parts of the page using random sampling.
  • SEM scanning electron microscope
  • by evaluation it has been determined that the alkaline reserve reached in the different sections of a book could be between 1% and 1.5%.
  • the invention process contemplates the possibility of automatic control by means of a robot.
  • the autoclave chamber where the dehydration is carried out may be used to recover library books or archive files that have experienced water or fire damage causing the pages to be stuck together.
  • the invention also provides a cellulosic material drying procedure that uses the invention equipment, and in which drying of the cellulosic material is carried out by means of intermittent cycles of evacuation and entry of hot air. For this, after the entry of the air it is heated for the amount of time necessary to reach a temperature of 50°C as a maximum, increasing the pressure within the autoclave because of the temperature rise.
  • the evacuation cycle can be carried out using a vacuum pump and a pressure sensor until a vacuum of between 30 and 40 millibars is reached.
  • the number of vacuum and air entry cycles is a function of the mass of cellulosic material to be dried.
  • the invention refers to the use of the invention equipment and the invention procedure for the treatment of cellulosic material, in general, and, in particular, books or any other type of publication on paper.
  • Figure 1 shows a machine that includes an equipment of the invention, which covers an autoclave (1); a solvent bottle (2) refrigerated/heated, provided with a jacket in which the solvent is stored, for example HFC 227; the heating is carried out by electrically supplied heating elements while the refrigeration is achieved using a compressor refrigerator; a residual solution collection tank (3) for the materials coming from the autoclave (1) by gravity, for the recovery of solvents by means of opening the pneumatic valve (NV5), activated by compressed air and on an automated program; the liquid and the neutralised free acids, as well as the solvent and the unconsumed reagent go down from the autoclave; a compressor unit (4) made up of a refrigerator-refrigerator with the aim of leading the solvent by distillation from the tank (3) to the solvent bottle (2), through cooling of the refrigeration jacket by the action of a condenser; an electric board (5); a condenser (6); a vacuum pump
  • Figures 2-4 show some of the specific achievements of the equipment provided by this invention with the equipment components in their assembled positions, with the symbols that follow the ISO and DIN standards for the identification of the machine components. These symbols are attached as addenda to Figure 4.
  • the invention equipment includes an autoclave (1) whose chamber is joined to a safety electrovalve (9) with an outflow valve to the atmosphere.
  • the chamber is of a cylindrical form having dimensions 540 x 360 (83 litres capacity) and is able to withstand a maximum pressure of 10 bar. The dimensions may vary according to the design and the volume needs.
  • the autoclave chamber has a heating system made up of heating bands covering part of the wall of the autoclave (1). It likewise has an external programmable temperature control sensor (TS), while in its interior there is another thermocouple (TC), to ensure that the temperature of the books does not exceed 40°C-50°C. It also has a pressure and vacuum sensor (PI).
  • the autoclave (1) has a safety valve (VS) which is released when the interior absolute pressure exceeds 6 bar.
  • a double effect rotary vacuum pump (7) with an estimated flow of 8 m 3 /h, allows achievement of more rapid dehydration of the cellulosic material before treatment.
  • the solvent refilling bottle (12) coupled to the system to refill the solvent bottle (2) when losses may have occurred during the process has a capacity of 60 litres of HFC 227, a fluorocarbon solvent classified as ecological since it contains no chlorine to damage the ozone layer, and it is not toxic, in fact it is used in asthma sprays.
  • the solvent bottle (2) is surrounded by a refrigerating jacket on which a cooling compressor unit(4) acts which is in turn joined to a hand operated valve.
  • a filter inserted which has a humidity absorption indicator to purify the recovered HFC 227.
  • a system with a heating band (10) encircles the recipient to effect the heating of the solvent liquid (2) and to facilitate pouring from the autoclave.
  • the solvent bottle (2) is situated on a loading cell (13) which allows dosification of the solvent through a program according to the different recipes prepared as a function of the weight of the books and of the deacidifying reagent added from the dosification tank.
  • the dosification of the solvent is controlled by weight.
  • the deacidification chamber is joined to a storage container (3) for the residual solution and from this solution the solvent is distilled to the solvent bottle (2) to start another work cycle.
  • this container (3) has a capacity of 90 litres, connected to the end of the autoclave (1) by means of a manual valve for cleaning operations; an electro-valve opens the evacuation circuit from the deacidification chamber to the distillation recipient when the impregnation time is finished of the reagent with the books contained in the deacidification chamber.
  • the chamber can be opened after the treatment and emptied and in this way a rapid drying of the treated books can be carried out.
  • a dosification tank (8) placed on loading cell (11), allows, through opening manual valves and an electrovalve by a program dosification of the reagent, whose composition is measured in the aforementioned container. Then, after the entry of the reagent into the chamber, a solution is made with the solvent that goes directly to the chamber from the solvent bottle (2).
  • autoclave (1) reception tank of the residual solution (3), bottle of HFC 227 (2), refill bottle of HFC 227 (12).
  • Te operation is as follows: The electrovalve EV1 (electrovalve) is opened, activated by the robot incorporated into the machinery , and then the pneumatic valve NV1 is opened, which connects the vacuum to the autoclave (1), until 30 mbar is reached, or by default a time of 4 minutes has passed, to attain an adequate vacuum. Once this time has passed, the output of the autoclave is opened, to break the vacuum by means of the electrovalve EV1, which allows a current of air to pass from the atmosphere to the autoclave (1).
  • the autoclave is at a temperature of 45-50°C
  • the air once the electrovalve EV1 is opened and the electrovalve EV2 is closed, that disconnects the vacuum, is held for 4-5 minutes until the temperature of the autoclave reaches(45-50°C).
  • the electrovalve EV1 shuts automatically once 4-5 minutes have passed and electrovalve EV2 and the pneumatic valve NV1 open once again, and a new vacuum cycle is produced again.
  • Successive openings and closures allows the passage of an air current and a pressure of 1 bar is obtained in the dehydration autoclave (1), which is at a temperature of 45°C.
  • the air is held in the chamber until this temperature is reached by an air residence time of about 4 minutes.
  • the vacuum pump B is connected by opening the electrovalve EV2, until 30-40 mbar is reached(some 3 or 4 minutes) and through the action of the programmed time EV2 closes to disconnect the vacuum produced by the pump and electrovalve EV1 opens again.
  • the total time of the operation of this cycle is about 8 minutes.
  • This cycle repeats 30 times to dehydrate 20 kg of books (4 hours).
  • the number of cycles is 40 for 30 kg of books (5 hours and 20 minutes), and 50 for 40 kg of books (6 hours and 40 minutes). In this way dehydration of the paper is achieved, going from a humidity content of 6-7% to approximately 2-2.5%.
  • This stage (see figure 6) is characterised by the dosification of the concentrated reagent arriving from tank (8), situated on a loading cell (11); tank outlets with manual valves remain open, and opened by the program controlled by the robot is activated pneumatic valve NV2, allowing the deacidifying reagent to pass to autoclave (1).
  • the reagent enters through the inlet of the bottom of autoclave (1), so that the concentrated reagent is not in contact initially with the matter to be treated, until it is diluted in solvent HFC 227. Dosification begins after the book dehydration ends.
  • the amounts of reagent added are previously programmed and calculated depending on the weights of the book to treat.
  • the calculation is performed according to the concentration of the deacidification reagent of tank (8), which depending on the batches and the prior factory analyses can be between 50-70% by weight.
  • concentration of the deacidification reagent of tank (8) which depending on the batches and the prior factory analyses can be between 50-70% by weight.
  • 800 g of reagent 100% would be required by the books to reach an alkaline reserve of between 1% and 2% corresponding to 1,150 g of concentrated solution, which is programmed into the robot.
  • Figure 7 presents the stage of the process at which the concentrated solution of the deacidifying reagent, deposited on the bottom of autoclave (1), is diluted by the solvent contained in tank (2) when it enters autoclave (1).
  • the diluent is HFC 227
  • tank (2) is situated on a loading cell (13), so that by a program the reagent is diluted to concentrations between 3.9% and 4.5 % depending on the acidity (pH measurement) of the material, for which 19.650 kg of solvent must be added.
  • the procedure involves activation of the loading cell, heating of tank (2) by starting the heating system formed by heating bands (10) on the bottom of tank (2) and which are powered by a suitable power source, a simultaneous opening of pneumatic valve NV7, so that the HFC 227 can flow from tank (2) to autoclave (1); pneumatic valves NV3, NV8 remain closed.
  • the reagent impregnation stage is effected as follows: from tank (8) with the evaluated reagent (concentration on the order of 70% by weight/weight of magnesium di-n-propylate carbonate), dissolved in n-propanol and HFC 227 the remaining 30%, by means of a loading cell it is automatically dosed according to the amount (in kg) of books placed in (1) which have been previously dehydrated.
  • pneumatic valve NV2 By weighing the quantities of reagent are introduced by a pneumatic valve NV2 which opens the circuit to the autoclave; after dosing of the amount by opening the manual valve of the HFC 227 tank and opening of pneumatic valve NV7, the number of kg programmed in the robot are entered.
  • pneumatic valve NV7 When the desired reagent concentration is reached which has been previously introduced in the robot according to the weight of the books and documents and their pH, pneumatic valve NV7 is automatically closed. Then the impregnation process begins, which lasts 3 hours as the carbonated reagent is less reactive than the corresponding uncarbonated magnesium n-propoxide. Diffusion is practically identical, thus ensuring homogeneity of the treatment, which is one of the differences with other current application methods.
  • Figure 8 shows the system used to empty the excess solution from the treatment, which is mainly HFC 227, excess reagent, an amount of glue dissolved by the HFC 227, dirt deposited on the books or documents and magnesium salts formed from the acid products extracted from the cellulosic materials.
  • the process takes place by opening pneumatic valve NV5, and passes through permanently open manual valve MV6.
  • a basic characteristic of this process is that it takes place quickly under the action of gravity and the simultaneous heating of autoclave (1) and cooling by the refrigeration system, passing the solution to tank (3) where it is stored until the start of the following stage of the process, which is recovery of the HFC 227.
  • Autoclave (1) can be then opened and the cellulosic material contained in it removed in order to introduce a new batch, to restart the dehydration process of figure 5.
  • processing time is gained as this is a variation which is claimed, given that there is no waiting time in the process as the solution passes in a few minutes from autoclave (1) to tank (3) since distillation is independent of the dehydration process, these occurring simultaneously.
  • Figure 9 shows the distillation stage for the solution stored in tank (3); it consists of heating said tank so that the solution arriving from the previous operation which has passed to this tank by heating of autoclave (1) to 45°C and by gravity due to the design of the tank situation; this last condition is very important to obtain a quick process.
  • tank (3) is heated by a resistance passing the HFC 227 to the solvent tank placed over the loading cell, obtaining as complete a recovery as possible of the solvent by refrigeration of bottle (2).
  • manual valves VM8 and VM10 are opened, as well as pneumatic valve NV3, so that the HFC 227 of tank (3) passes to the solvent tank (2) which is refrigerated by compressor C, which is functioning and connected to the manual valve to allow refrigeration of said tank.
  • Pneumatic valves NV6, NV5, NV7, NV4 and NV6 remain closed, as well as manual valve VM9, to conduct the HCF 227 to tank (2).
  • the distillation process lasts around 6-7 hours and occurs simultaneously to dehydration of the books, which lasts depending on the weight of the books 4 hours, 5 hours and 20 minutes, and 6 hours and 40 minutes, respectively, for 20, 30 and 40 kg of books. When the distillation is considered to have finished the system is ready for the next stage of the process.
  • tank (3) In tank (3) remain sludge and residues of the acidity soluble and dirt carried by the HCF 227 from the treated books. IN addition remains the n-propanol, which has a low vapour pressure compared to HFC 227, and is therefore not distilled although a small amount is carried along, which as well as the humidity is retained by filter F1.
  • tank (3) is cleaned by opening manual valve MV5, letting in n-propanol, keeping open manual valve MV6, in its normal position, and air is allowed to enter causing a gurgling which stirs the residue with the added solvent. Then manual valve MV7is opened as shown in figure 10, thereby removing residue left from the operational cycles.
  • Tank (2) is refrigerated as shown in the schematic by starting compressor-condenser C-R.
  • the compressor and cold generating system together with a heat dissipation system is driven by a motor M which drives a fan (V).
  • the insulating jacket condenses the water and has a condensate outlet electrovalve in a de-icing process, which takes place after cooling of the liquid in tank (2).
  • the first is photocopying paper for inkjet printers (Inapa Multioffice) with 80 g/m 2 density, DIN A4 with a 0.11 mm thickness and pH of 7.65; notebook paper with a density of 71.3 g/m 2 initially and an acidic pH of 5.33; paper from the book "Enciclopedia Catalana” with an initial density of 57.5 g/m 2 and an untreated paper pH of 6.29.
  • the amount of paper treated was 25 kg in the 83 1 capacity autoclave.

Landscapes

  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Paper (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Processing Of Solid Wastes (AREA)
EP00931289A 1999-05-27 2000-05-26 Device and method for mass deacidification, elimination of free acidity of cellulosic material Expired - Lifetime EP1245733B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ES9901152 1999-05-27
ES009901152A ES2154592B1 (es) 1999-05-27 1999-05-27 Equipo y procedimiento para la desacidificacion en masa, eliminacion de la acidez libre y desinfestacion de materiales celulosicos.
PCT/ES2000/000188 WO2000073584A1 (es) 1999-05-27 2000-05-26 Equipo y procedimiento para desacidificacion en masa, eliminacion de la acidez libre y desinfestacion de materiales celulosicos

Publications (2)

Publication Number Publication Date
EP1245733A1 EP1245733A1 (en) 2002-10-02
EP1245733B1 true EP1245733B1 (en) 2006-03-29

Family

ID=8308592

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00931289A Expired - Lifetime EP1245733B1 (en) 1999-05-27 2000-05-26 Device and method for mass deacidification, elimination of free acidity of cellulosic material

Country Status (12)

Country Link
US (1) US7211221B1 (pt)
EP (1) EP1245733B1 (pt)
AT (1) ATE321912T1 (pt)
AU (1) AU4927100A (pt)
BR (1) BR0011003B1 (pt)
CA (1) CA2375056C (pt)
DE (1) DE60026989T2 (pt)
DK (1) DK1245733T3 (pt)
ES (2) ES2154592B1 (pt)
MX (1) MXPA01012273A (pt)
PT (1) PT1245733E (pt)
WO (1) WO2000073584A1 (pt)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10139517A1 (de) 2001-08-10 2003-02-20 Peter Zitzmann Verfahren und Vorrichtung zum Entsäuern von Büchern
US20090152093A1 (en) * 2004-11-29 2009-06-18 Frederick William Millar Liquid treatment device and method
SK287845B6 (sk) 2007-09-18 2012-01-04 Stu Fakulta Chemickej A Potravinarskej Technologie Multifunction device for modification of cellulose materials and method for modification of cellulose materials
DE102015107863A1 (de) * 2015-05-19 2016-11-24 GSK mbH - Gesellschaft zur Sicherung von schriftlichem Kulturgut mit beschränkter Haftung Vorrichtung und Verfahren zur Entfernung von Verunreinigungen und zur Desinfektion von Archivalien
CN106192573A (zh) * 2016-07-27 2016-12-07 陕西天洁净型煤化工技术开发有限公司 一种适用于纸质文献批量脱酸的装置和方法
CN108004847B (zh) * 2017-11-28 2021-08-10 华南理工大学 一种古籍脱酸修复方法
CN112391873B (zh) * 2019-08-16 2021-11-23 鼎纳科技有限公司 一种大型图书脱酸设备及其控制系统
CN111335072B (zh) * 2020-04-02 2023-11-14 杭州众材科技股份有限公司 立式纸品脱酸装置及纸品脱酸机
CN112371066A (zh) * 2020-11-03 2021-02-19 北京康欣东弘医药科技有限公司 一种注射微球的制备系统
CN113201969B (zh) * 2021-05-14 2022-10-11 杭州众材科技股份有限公司 一种智能纸张脱酸系统

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4860685A (en) * 1985-07-10 1989-08-29 Smith Richard D Treatment of cellulosic materials
CA1328460C (en) * 1988-09-30 1994-04-12 Conrad William Kamienski Mass treatment of cellulosic materials
DE3904111A1 (de) * 1989-02-11 1990-08-16 Battelle Institut E V Verfahren und vorrichtung zur umweltfreundlichen massenentsaeuerung von buechern und anderen papiererzeugnissen
WO1991004800A1 (en) * 1989-10-02 1991-04-18 Fmc Corporation Book deacidification method and apparatus
US5173258A (en) * 1989-10-11 1992-12-22 American Sterilizer Company Recirculation, vapor and humidity control in a sealable enclosure
US5213619A (en) * 1989-11-30 1993-05-25 Jackson David P Processes for cleaning, sterilizing, and implanting materials using high energy dense fluids
US5122344A (en) * 1990-01-31 1992-06-16 Mdt Corporation Chemical sterilizer system
US5282320A (en) * 1991-08-23 1994-02-01 Fmc Corporation Book drying process
ES2125792B1 (es) 1996-01-05 1999-11-16 Univ Catalunya Politecnica Equipo y procedimiento para desacidificacion, desinfestacion y desinfeion en masa de documentos y libros.

Also Published As

Publication number Publication date
BR0011003A (pt) 2002-04-02
AU4927100A (en) 2000-12-18
ES2260014T3 (es) 2006-11-01
ES2154592B1 (es) 2001-10-16
ATE321912T1 (de) 2006-04-15
EP1245733A1 (en) 2002-10-02
WO2000073584A1 (es) 2000-12-07
DK1245733T3 (da) 2006-06-06
CA2375056A1 (en) 2000-12-07
MXPA01012273A (es) 2003-06-24
ES2154592A1 (es) 2001-04-01
DE60026989D1 (de) 2006-05-18
DE60026989T2 (de) 2006-12-21
PT1245733E (pt) 2006-07-31
BR0011003B1 (pt) 2011-11-29
US7211221B1 (en) 2007-05-01
CA2375056C (en) 2009-10-13

Similar Documents

Publication Publication Date Title
EP1245733B1 (en) Device and method for mass deacidification, elimination of free acidity of cellulosic material
US3989461A (en) Apparatus for use, recovery, reconstitution, and recyclization of sterilant gas mixture
US5120500A (en) Process and device for nonpolluting mass deacidification of books and other paper products
CN108914701B (zh) 一种可批量用于整册古籍脱酸增强加固装置
KR100518934B1 (ko) 진공세척 건조장치 및 방법
CA2727805C (en) Apparatus for impregnating fibrous material with a liquid
CN101954368A (zh) 医疗废物无害化处理装置
Hubbe et al. Nonaqueous Solution Deacidification Treatments to Prolong the Storage Life of Acidic Books: A Review of Mechanistic and Process Aspects.
JPH05500473A (ja) 揮発性成分を有する液体組成物のための放出制御システム及びその方法
AU2009200812B2 (en) Battery recycling
CN207736762U (zh) 一种用于3d打印机的供料装置
CN217599064U (zh) 用于贴标签机的热胶装置、贴标签机和容器处理设施
JP2009500504A (ja) 炭化水素を含有する製品を処理する方法及び装置
CN100412723C (zh) 图像删除装置和图像删除方法
US4054692A (en) Method of impregnating and drying materials and installations for carrying out this method
CN212833140U (zh) 一种化工废液回收装置
CN115239233A (zh) 物流装卸消毒追踪系统
JP2023548567A (ja) 連続要素除染及び滅菌システム
KR102251696B1 (ko) 유기성 폐기물을 이용한 사료 및 비료 제조시스템
US20230242845A1 (en) Indoor food waste fermentation and recycling process
US1670727A (en) Process and apparatus for converting carbohydrates
KR100933876B1 (ko) 폴리염화비페닐이 함유된 폐유가 수용된 폐기기의 재활용시설
US20200189222A1 (en) Aerosol recycling process and system
US11491490B1 (en) Organic waste management system
EP4342844A1 (en) Hydrogen production process

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20011220

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 20041014

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RTI1 Title (correction)

Free format text: DEVICE AND METHOD FOR MASS DEACIDIFICATION, ELIMINATION OF FREE ACIDITY OF CELLULOSIC MATERIAL

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060329

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060329

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60026989

Country of ref document: DE

Date of ref document: 20060518

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060531

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Effective date: 20060608

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20060402195

Country of ref document: GR

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2260014

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20070102

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20080530

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20080522

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20080512

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060329

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20080530

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090526

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090526

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090527

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20120530

Year of fee payment: 13

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 60026989

Country of ref document: DE

Representative=s name: GRUENECKER, KINKELDEY, STOCKMAIR & SCHWANHAEUS, DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 60026989

Country of ref document: DE

Representative=s name: GRUENECKER, KINKELDEY, STOCKMAIR & SCHWANHAEUS, DE

Effective date: 20130812

Ref country code: DE

Ref legal event code: R081

Ref document number: 60026989

Country of ref document: DE

Owner name: PAL PRESERVATION ACADEMY GMBH LEIPZIG, DE

Free format text: FORMER OWNER: UNIVERSITAT POLITECNICA DE CATALUNYA, TERRASSA, ES

Effective date: 20130812

Ref country code: DE

Ref legal event code: R081

Ref document number: 60026989

Country of ref document: DE

Owner name: GESCHKE, ALEXANDER OTTOMAR MARTIN, DE

Free format text: FORMER OWNER: UNIVERSITAT POLITECNICA DE CATALUNYA, TERRASSA, ES

Effective date: 20130812

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20131119

Year of fee payment: 14

Ref country code: GB

Payment date: 20131120

Year of fee payment: 14

Ref country code: IE

Payment date: 20131126

Year of fee payment: 14

Ref country code: PT

Payment date: 20130527

Year of fee payment: 14

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

Effective date: 20130531

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20131126

Year of fee payment: 14

Ref country code: NL

Payment date: 20131119

Year of fee payment: 14

Ref country code: LU

Payment date: 20131202

Year of fee payment: 14

Ref country code: BE

Payment date: 20131121

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130531

REG Reference to a national code

Ref country code: PT

Ref legal event code: MM4A

Free format text: LAPSE DUE TO NON-PAYMENT OF FEES

Effective date: 20141126

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20141201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140526

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20140526

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141126

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 60026989

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20150130

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 60026989

Country of ref document: DE

Owner name: PAL PRESERVATION ACADEMY GMBH LEIPZIG, DE

Free format text: FORMER OWNER: GESCHKE, ALEXANDER OTTOMAR MARTIN, 16348 WANDLITZ, DE

Effective date: 20150202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140526

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140526

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140526

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140602

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140531

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20180510

Year of fee payment: 19

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60026989

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191203